红土镍矿硫酸熟化焙烧—水浸浸出液中回收镍钴等有价金属的研究
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摘要
随着可用于火法处理的含镍钴的硫化矿逐渐枯竭,使得适用于湿法处理的红土镍矿的研究已经受到了越来越多的关注。经过不同的湿法浸出过程,镍、钻、锰、铁、铬、铝等金属以金属盐的形式进入浸出液中,因此,采取一种经济合理的除杂流程以回收其中的镍钴等有价金属对于整个红土镍矿的处理过程具有重要的意义。
本研究对象为对来自菲律宾的褐铁矿型红土镍矿采用硫酸熟化焙烧-水浸工艺处理得到的多金属离子溶液。分析溶液的成分表明浸出液中Fe3+、A13+含量高,且同时存在不同含量的Cr3+、Zn2+、Cu2+Ca2+、Mg2+、Mn2+等杂质离子。针对浸出液成分复杂,杂质离子多的特点,对比不同方法的优缺点,本研究采用水解沉淀分离Fe3+、A13+、Cr3+-氟化盐沉淀分离Ca2+、Mg2+-硫化沉淀分离Zn2+、Cu2+-氧化沉淀分离Mn2+的四步法分离其中的杂质离子,得到了较纯净的含Ni2+Co2+及少量金属离子杂质的溶液。
通过单因素实验确定了各步的最佳工艺,并得到了最优的实验结果。采用水解共沉淀的方法分离Fe3+、A13+、Cr3+,在优化条件下,Fe3+、A13+、Cr3+的沉淀率分别为99.6%、99.4%、92.2%,溶液中剩余的Fe3+、A13+、Cr3+浓度分别低于0.05g/L、0.03 g/L及0.04 g/L。采用氟化盐沉淀法分离Ca2+、Mg2+,钙镁的沉淀率分别可达到88.91%和93.07%,溶液中的Ca2+、Mg2+浓度可降至0.03g/L和0.07g/L以下采用硫化沉淀法分离了其中的Zn2+、Cu2+,锌铜的沉淀率分别可达到99.5%和99.9%以上,溶液中剩余Zn2+、Cu2+的浓度分别低于0.002g/L和0.001g/L。最后通过氧化沉淀法分离了溶液中的Mn2+,沉淀率为99.9%以上,溶液中残余的Mn2+浓度低于0.004g/L。最后得到的为含Ni2+、Co2+以及少量金属离子杂质的溶液。整个流程镍钴的回收率分别可达到90%和85%以上。
本研究针对原料特点,确定了各工艺的最优工艺条件,为工业化生产实践提供了技术方案。
With the depletion of the nickel and cobalt contained sulfide ore which is easy treated by pyrometallurgical processes, more attentions have been paid on the treating of nickel laterite by hydrometallurgical processes. After different leaching processes, the leaching solution is obtained which contains nickel, cobalt, manganese, iron, chromium, aluminum and other metals in the form of metal salts. To recover the valuable metals like nickel and cobalt, a reasonable and economical method to separate the impurities and purify the leaching solution has a great significance for the whole treating processes of nickel laterite.
In this research, a mixed metal ions solution was treated which was obtained from Philippines nickel laterite using concentrated sulfuric acid curing-roasting-leaching processes. By analyzing the constitution of the leaching solution, results showed that there have a high content of Fe3+,Al3+and Mn2+ions in the solution while the content of Cr3+,Zn2+,Cu2+,Ca2+,Mg2+ ions and other impurities was realitivily low. For the complex composition of the solution, a four-step precipitataion mehod was taken by comparing different methods, including the remove of Fe3+, Al3+ and Cr3+ ions by hydrolysis co-precipitation, remove of Ca2+ and Mg2+ ions by fluoride precipitation, remove of Zn2+and Cu2+ ions by sulfide precipitation and the remove of Mn2+ions by oxidation precipitation. After the precipitation and separation of impurities, a pure solution which contained Ni2+ and Co2+ ions and little impurities was obtained.
By adoption of single factor experiments, optimum technical conditions were determined while the optimumexperiment results wereobtained. Using hydrolysis precipitation mehod to remove Fe3+,Al3+and Cr3+ ions, under optimum conditions, the removal rate were 99.6%,99.4% and 92.2%,respectivelly. Remained concentration of Fe3+,Al3+ and Cr3+ ions in the solution were lower than0.05g/L,0.03 g/L and 0.04 g/L, respectively. By utilizing fluoride precipitation method to remove Ca2+ and Mg2+ ions, precipitation rate of Ca2+ and Mg2+ can reach88.91% and 93.07%, remained concentration of Ca2+ and Mg2+ ions in the solution can be recuced to 0.03g/L and 0.07g/L. Using sulfide precipitation method to remove Zn2+and Cu2+ ions,99.9% of Cu2+ and 99.5% of Zn+ can be precipitated and separated from the solution, remained concentration of Zn2+and Cu2+ ions were lower than 0.002g/L and 0.001g/L. Oxidation precipitation method was adopted to remove Mn2+ ions in the solution at last. Precipitaion rate of Mn2+ was higher than 99.9%, remained concentration of Mn2+ in the solution was lower than 0.004g/L. After the precipitation and separation processes, the solution which contained Ni2+ and Co2+ ions and trace impurities was ontained. Through the entire processes, more than 90% of nickel and 85% of cobalt can be recoverd from the solution.
According to the characteristics of the materials, the present work determined the optimum technical conditions for each process,which will contribute a techincal scheme to the industrialized practice and production.
本研究对象为对来自菲律宾的褐铁矿型红土镍矿采用硫酸熟化焙烧-水浸工艺处理得到的多金属离子溶液。分析溶液的成分表明浸出液中Fe3+、A13+含量高,且同时存在不同含量的Cr3+、Zn2+、Cu2+Ca2+、Mg2+、Mn2+等杂质离子。针对浸出液成分复杂,杂质离子多的特点,对比不同方法的优缺点,本研究采用水解沉淀分离Fe3+、A13+、Cr3+-氟化盐沉淀分离Ca2+、Mg2+-硫化沉淀分离Zn2+、Cu2+-氧化沉淀分离Mn2+的四步法分离其中的杂质离子,得到了较纯净的含Ni2+Co2+及少量金属离子杂质的溶液。
通过单因素实验确定了各步的最佳工艺,并得到了最优的实验结果。采用水解共沉淀的方法分离Fe3+、A13+、Cr3+,在优化条件下,Fe3+、A13+、Cr3+的沉淀率分别为99.6%、99.4%、92.2%,溶液中剩余的Fe3+、A13+、Cr3+浓度分别低于0.05g/L、0.03 g/L及0.04 g/L。采用氟化盐沉淀法分离Ca2+、Mg2+,钙镁的沉淀率分别可达到88.91%和93.07%,溶液中的Ca2+、Mg2+浓度可降至0.03g/L和0.07g/L以下采用硫化沉淀法分离了其中的Zn2+、Cu2+,锌铜的沉淀率分别可达到99.5%和99.9%以上,溶液中剩余Zn2+、Cu2+的浓度分别低于0.002g/L和0.001g/L。最后通过氧化沉淀法分离了溶液中的Mn2+,沉淀率为99.9%以上,溶液中残余的Mn2+浓度低于0.004g/L。最后得到的为含Ni2+、Co2+以及少量金属离子杂质的溶液。整个流程镍钴的回收率分别可达到90%和85%以上。
本研究针对原料特点,确定了各工艺的最优工艺条件,为工业化生产实践提供了技术方案。
With the depletion of the nickel and cobalt contained sulfide ore which is easy treated by pyrometallurgical processes, more attentions have been paid on the treating of nickel laterite by hydrometallurgical processes. After different leaching processes, the leaching solution is obtained which contains nickel, cobalt, manganese, iron, chromium, aluminum and other metals in the form of metal salts. To recover the valuable metals like nickel and cobalt, a reasonable and economical method to separate the impurities and purify the leaching solution has a great significance for the whole treating processes of nickel laterite.
In this research, a mixed metal ions solution was treated which was obtained from Philippines nickel laterite using concentrated sulfuric acid curing-roasting-leaching processes. By analyzing the constitution of the leaching solution, results showed that there have a high content of Fe3+,Al3+and Mn2+ions in the solution while the content of Cr3+,Zn2+,Cu2+,Ca2+,Mg2+ ions and other impurities was realitivily low. For the complex composition of the solution, a four-step precipitataion mehod was taken by comparing different methods, including the remove of Fe3+, Al3+ and Cr3+ ions by hydrolysis co-precipitation, remove of Ca2+ and Mg2+ ions by fluoride precipitation, remove of Zn2+and Cu2+ ions by sulfide precipitation and the remove of Mn2+ions by oxidation precipitation. After the precipitation and separation of impurities, a pure solution which contained Ni2+ and Co2+ ions and little impurities was obtained.
By adoption of single factor experiments, optimum technical conditions were determined while the optimumexperiment results wereobtained. Using hydrolysis precipitation mehod to remove Fe3+,Al3+and Cr3+ ions, under optimum conditions, the removal rate were 99.6%,99.4% and 92.2%,respectivelly. Remained concentration of Fe3+,Al3+ and Cr3+ ions in the solution were lower than0.05g/L,0.03 g/L and 0.04 g/L, respectively. By utilizing fluoride precipitation method to remove Ca2+ and Mg2+ ions, precipitation rate of Ca2+ and Mg2+ can reach88.91% and 93.07%, remained concentration of Ca2+ and Mg2+ ions in the solution can be recuced to 0.03g/L and 0.07g/L. Using sulfide precipitation method to remove Zn2+and Cu2+ ions,99.9% of Cu2+ and 99.5% of Zn+ can be precipitated and separated from the solution, remained concentration of Zn2+and Cu2+ ions were lower than 0.002g/L and 0.001g/L. Oxidation precipitation method was adopted to remove Mn2+ ions in the solution at last. Precipitaion rate of Mn2+ was higher than 99.9%, remained concentration of Mn2+ in the solution was lower than 0.004g/L. After the precipitation and separation processes, the solution which contained Ni2+ and Co2+ ions and trace impurities was ontained. Through the entire processes, more than 90% of nickel and 85% of cobalt can be recoverd from the solution.
According to the characteristics of the materials, the present work determined the optimum technical conditions for each process,which will contribute a techincal scheme to the industrialized practice and production.
引文
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